Transition metal catalyzed cooligomerizations of alpha, omega-diynes with monoacetylenes, nitriles and isonitriles will be explored as crucial steps in the synthesis of molecules of physiological interest. A recent synthesis of polycycles with extensive control of substitution, stereochemistry and structural topology based on this approach starting with specifically substituted 1,5-hexadiynes will be extended to a highly versatile synthesis of A-ring aromatic steroids. This approach furnishes a potential control of A ring substitution, control of all stereochemistry, incorporation of heteroatomic moieties, and capabilities in nor- and homosteroidal synthesis. A general synthesis of substituted anthraquinones will be applied to anthracyclinone synthesis. A general synthesis of the isoquinoline nucleus based on the acetylene cyclization principle will be extended. Scope and limitations as well as mechanistic aspects are currently under investigation. New approaches to quinoline, pyrrole, thiophene and furan heterocycles will be initiated. BIBLIOGRAPHIC REFERENCES: K. P. C. Vollhardt, Transition Metal Catalyzed Acetylene Cyclizations in Organic Synthesis, Acc. Chem. Res., 10, (1977) in press. R. L. Hillard III and K. P. C. Vollhardt, Substituted Benzocyclobutenes, Indans, and Tetralins Via Cobalt Catalyzed Cooligomerization of alpha, omega-Diynes with Substituted Acetylenes. Formation and Synthetic Utility of Trimethylsilylated Benzocycloalkenes, J. Amer. Chem. Soc., 99, (1977), in press.